N-hydroxyalkyl acrylamides

ABSTRACT

N-3-Hydroxyalkyl acrylamides, and substituted derivatives thereof, are prepared by (1) reduction of an N-3-oxohydrocarbonsubstituted acrylamide, (2) addition of an alcohol to the N-3oxohydrocarbon-substituted acrylamide, followed by hydrogenation of the carbonyl group and elimination of the alcohol, or (3) hydrolysis of a 2-vinyl-5,6-dihydro-1,3-oxazine. The acrylamides are useful as monomers for conversion to polymers (which may also be prepared by reduction of the corresponding oxohydrocarbonsubstituted acrylamide polymers) with a number of interesting properties, including utility as membranes for desalination of water by hyperfiltration. The polymers may be crosslinked by the action of such reagents as diisocyanates, dicarboxylic acid halides, and aldehydes in acidic solution.

United States Patent 1 1 Hoke [ Aug. 5, 1975 1 1 N-HYDROXYALKYL ACRYLAMIDES Donald Irvin Hoke, Chagrin Falls,

Ohio

173] Assignec: The Lubrizol Corporation,

Cleveland, Ohio [22] Filed: Oct. 20, 1972 121] Appl. No.: 299,539

Related U.S. Application Data [60] Division of Scrv No. 51.712, July 1, 1970, Pat. No. 3.729.456. which is a continuation-in-part of Ser. No. 788.820. July 3, 1969. Pat. No. 3,585,125. which is a continuation-in-part of Ser. No. 713,787, March 18, 1968. abandoned.

[75] Inventor:

I52] U.S. Cl 260/561 N [51] Int. Cl. C07c 103/30 [58] Field of Search 260/561 N [56] References Cited UNlTED STATES PATENTS 3,277,056 10/1966 Coleman 260/561 N X 3,425.942 2/1969 Coleman... 260/561 N X 3.454669 7/1969 Lauclise 260/561 N X 3.531.525 9/1970 Hoke et a1. 260/561 3,649,688 3/1972 Gordon et a1 260/561 N 3.729.456 4/1973 Hoke 260/561 N X OTHER PUBLICATIONS Chem. Abstracts, Taylor, 60:4262d.

Chem. Abstracts, Luskin et al., 55:19960c.

Chem. Abstracts. .ledlinski et al., 66:6503 8a.

Primary E,\'aminerLewis Gotts Assistant Examiner-Ethel G. Love Attorney, Agent, or Firm-James W. Adams, Jr.; William H. Pittman 1 5 7 ABSTRACT N-3-Hydroxyalkyl acrylamides, and substituted derivatives thereof, are prepared by 1) reduction of an N-3- oxohydrocarbon-substituted acrylamide, (2) addition of an alcohol to the N-3-oxohydrocarbon-substituted acrylamide, followed by hydrogenation of the carbonyl group and elimination of the alcohol, or (3) hydrolysis of a 2-viny1-5,6-dihydro-l,3-oxazine. The acrylamides are useful as monomers for conversion to polymers (which may also be prepared by reduction of the corresponding oxohydrocarbon-substituted acrylamide polymers) with a number of interesting properties. including utility as membranes for desalination of water by hyperfiltration. The polymers may be crosslinked by the action of such reagents as diisocyanates, dicarboxylic acid halides, and aldehydes in acidic solution.

14 Claims, 2 Drawing Figures .1 N-HYDROXYALKYL ACRYLAMIDES SUMMARY OF THE INVENTION This invention relates to new compositions of matter, both monomeric and polymeric. More particularly, it relates to novel N-3-hydroxyalkyl acrylamides of the formula wherein R is a hydrocarbon or substituted hydrocarbon radical; each of R R, R and R is individually hydrogen or a hydrocarbon or substituted hydrocarbon radical; and R" is hydrogen, halogen or a lower alkyl or substituted lower alkyl radical; and polymers of said compounds. The invention further relates to a novel method for removal of dissolved impurities from water by hyperfiltration through a membrane comprising a polymer of an N-3-hydroxyalkyl acrylamide.

The term hydrocarbon radical as used herein includes aliphatic, cycloaliphatic and aromatic (including aliphaticand cyeloaliphatic-substituted aromatic and aromatic-substituted aliphatic and cyeloaliphatic) radicals. It also includes cyclic radicals wherein the ring is completed through another portion of the molecule; that is, any two indicated substituents may together form a cycloalkyl radical.

The following are illustrative of hydrocarbon radicals within the scope of this invention. Where a named radical has several isomeric forms (e.g., butyl), all such forms are included.

Methyl Ethyl Propyl Butyl Benzyl Cyclohexyl Cyclopentyl Methylcyclopentyl Hexyl Octyl Decyl Vinyl Allyl Ethynyl Propargyl Phcnyl Tolyl Xylyl Cyclopentadienyl Vinylphenyl lsopropenylphenyl Cinnamyl Naphthyl vention.

Many obvious variations of these radicals will be apparent to those skilled in the art and are included within the scope of the invention.

Substituted hydrocarbon, alkyl, aryl, etc., radicals are considered fully equivalent to the hydrocarbon, alkyl, aryl, etc., radicals and to be part of this invention. By substituted is meant radicals containing substituents which do-not alter significantly the character or reactivity of the radical. Examples are:

Halide (fluoride, chloride, bromide, iodide) Hydroxy Ether (especially lower alkoxy) Keto Ester (especially lower carbalkoxy) Aminoacyl (amide) Nitro Mercapto Thioether Sulfoxy Sulfone I In general, no more than about three such substituent groups will be present for each 10 carbon atoms in the radical.

Preferably, the hydrocarbon or substituted hydrocarbon radicals in the compounds of this invention are free from ethylenic and aeetylenic unsaturation and have no more than about 30 carbon atoms, desirably no more than about 12 carbon atoms. A particular preference is expressed for lower hydrocarbon radicals, the word lower" denoting radicals containing up to seven carbon atoms. Still more preferably, they are lower alkyl or aryl radicals, most often alkyl. In the most preferred compounds of this invention, R, R and R are alkyl radicals, especially lower alkyl radicals; R is hydrogen or an alkyl radical; R is hydrogen; and R is hydrogen or methyl.

THE MONOMERS The following are illustrative compounds of this inv N-( l. l -Dimethyl-3-hydroxybutyl )aerylamide CH, o

'CH HCH- NHCCH=CH2 OH CH,

'N-( 1,l-Dimethyl-3 hydroxybutyl .imethacrylamide N-( l l -Diethyl-2-methyl-3-hydroxypcntyl )acrylamide N-( l ,3-Diphenyll -methyl-3-hydroxypropyl )acrylamide N-[ l,3-Di-( p-chlorophenyl l -methyl-3- hydroxypropyl ]methacrylamide N-( l-Methyl-3-hydroxybutyl )-2-chloroacrylamide OH CH" The compounds of this invention may be prepared by the reduction of N-3-oxohydrocarbon-substituted aerylamides, which are described in US. Pat. Nos. 3,277,056 and 3,425,942, the disclosures of which are incorporated by reference herein. The reduction method must be one which reduces the carbonyl group but which does not at the same time reduce the olefinic bond. Preferred methods for accomplishing this are reduction with sodium borohydride and the Meerwein- Ponndorf-Verley reaction, which involves hydrogen interchange between the oxo group and a lower aliphatic alcohol in the presence of a metal alkoxide. These methods are well known in the art in their general application, and are not believed to require extended discussion.

A preferred method for converting an N-3- oxohydrocarbon-substitutcd acrylamide into an N-3- hydroxyalkyl acrylamide involves the preparation of a lower alkoxypropionamidc by reaction of the N-3- oxohydrocarbon-substituted acrylamidc with a lower 4 alkanol in the presence of a strongly'alkalinecatalyst, followed by reduction of the carbonyl group and'removal of the lower alkoxy group, typically by pyrolysis in contact with strong alkali. The first step in this reaction sequence, the preparation of the lower alkoxypropionamide, is described in detail in copending applica' tion Ser. No. 15,855, filed Mar. 2, 1970, now US. Pat. 3,647,875, the pertinent disclosure of which is incorporated by reference herein.

In the second step, the carbonyl group of the N-3- oxohydrocarbon-substituted alkoxypropionamide is reduced to a carbinol group, ordinarily by hydrogen in the presence of v a suitable hydrogenation catalyst. (Other methods of reduction can be used, but the chief advantage of this method is that it makes possible ordinary hydrogenation without danger of reducing the olefinie bond of the acrylamide.) Typical catalysts which may be used are palladium, platinum and Raney nickel; Raney nickel is preferred.

Following reduction of the carbonyl group, the alkoxy group is removed by any of several methods which are known per se. Typical methods are described briefly in a recent review: P. F. Butskus et al.. Russian Chemical Reviews, 35, 839 (1966). The preferred method is pyrolysis of the alkoxy 'compound in the presence of a basic reagent. ordinarily a strong base such as solid sodium hydroxide, at about -2()0C. This reaction is conveniently carried out at reduced pressure,

Still another method for the preparation of the N-3- hydroxyalkyl acrylamides ofthis invention is by hydrolysis of a 2-vinyl-5,6-dihydrol .3-oxazine such as is described in US. Pat. No. 2,968,657. Oxazines of this type may be prepared by the reaction of an unsaturated nitrile with a l,3- or 2,4-alkanediol or an oxetane; they are represented by the formula wherein R are as described above. The hydrolysis is conveniently carried out in alkaline solution in a suitable polar organic solvent such as an alcohol, ketone. ether, or the like. The reaction temperature is ordinarily about 50lO0C.

The preparation of the N-3-hydroxyalkyl acrylamides is illustrated by the following examples.

EXAMPLE I To a solution of 4070 grams (24 moles) of N-( 1,1- dimethyl-B-oxobutyl)aerylamide (diacetone acrylamide) in about 6000 grams of methanol is added a solution of sodium methoxide prepared from 54 grams (2.4 moles) of sodium in about 144 grams of methanol. (A total of 192 moles of methanol is used.) The resulting solution is heated under reflux for 6V2 hours, and then grams of sulfuric acid is added. followed by a few grams of acetic acid to neutralize the mixture. The

methanolic solution is filtered and the methanol is removed by distillation under reduced pressure. There is obtained 4535.8 grams (94% of the theoretical amount) of N-( l.l-dimcthyl-3-oxobutyl) 3-methoxypropionamidc. The product is a clear liquid.

A solution of 490 grams of N-( l,l-dimethyl-3- oxobutyl) 3-methoxypropionamidc in 320 grams of methanol is purged with nitrogen, and 28.2 grams of Raney nickel is added. The mixture is pressurized with hydrogen in an autoclave at ll5() psi. and heated to 49C., and then to 72C. over 45 minutes. After heating at 72C. for an additional 3V2 hours. with periodic restoration of the 1 I50 psi. hydrogen pressure, the Raney nickel is removed by filtration and the methanol is stripped. There is obtained 475 grams of N-( l.ldimethyl-3-hydroxybutyl )-3-methoxypropionamide, which is allowed to drip onto sodium hydroxide pellets heated at l6()l70C. in a glass tube which has been evacuated to a pressure of mm. The system is maintained under nitrogen during the reaction. The product is N-( l. l -dimethyl3-hydroxybutyl )acrylamide.

EXAMPLE 2 The procedure of Example I is repeated, except that the diaeetonc acrylamide is replaced by an equimolar amount of N-( l.3-diphcnyl-l-methyl-3-oxopropyl)acrylamide. The product is N-( l .3-diphcnyl-l-methyl-3- hydroxypropyl )acrylamide.

EXAMPLE 3 A solution of 338 grams (2 moles) of diacetone acrylamide and 224 grams (1.1 mole) of aluminum isopro poxide in 350 ml. of isopropyl alcohol is heated in a reaction vessel fitted with a distillation column. Distillate is removed slowly and tested for the presence of acetone. After l5() ml. of distillate has been collected. an additional 50 ml. of isopropyl alcohol is added. and nine further 50-ml. increments are added during the 28-hour distillation period. At the end of this time, a negative test for acetone is obtained on the distillate. The solution is then cooled to room temperature. and 280 ml. of concentrated hydrochloric acid and 500 ml. of water are added. The solution is extracted with five ZOO-ml. portions of benzene and the benzene solution is dried over calcium sulfate and distilled. The desired N-( l .l-dimethyl-3-hydroxybutyl)acrylamide is obtained as the distillate.

EXAMPLE 4 A mixture of 5 grams of 2-vinyl-4.4.b-trimethyl-S.6- dihydro-l.3-oxazine. 25 grams of dioxane, 25 ml. of water. 2.5 ml. of 20% aqueous sodium hydroxide solution. and 0.] gram of N-phenyl-B-naphthylamine (as a polymerization inhibitor) is purged with nitrogen and heated to 80C.. with stirring. for 7 hours. Upon neutralization of the reaction mixture and removal of the volatile materials. there is obtained an 88% yield of the desired N-( l. l -di|neth \l-3hydroxybutyl )acrylamide.

EXAMPLE 5 A mixture of IO grams of 2-vinyl-- -4.4.o-trimethyl-5.o-dihydro-l.3-oxazine. grams of tertiary butyl alcohol. 25 grams of water. 1 ml. of 2071 sodium hydroxide and 0.1 gram of N-phenyl-[B- naphthylamine is heated to 80C.. with stirring. for 7% hours. Upon neutralization ofthe reaction mixture and removal of the solvents. there is obtained a 62.57: yield of N-( l l -dimeth vl-3-hydroxybutyl )acrylamide.

EXAMPLE 6 To a solution of 2.5 grams of sodium borohydride in ml. of water is added, over a /2 hour period, 42.3 grams of diacetone acrylamidc. The reaction is exothermic and the temperature rises to about 40C. during the addition. The mixture is stirred for one hour. and is then saturated with sodium chloride and extracted with five lOO-ml. portions of chloroform. The extracts are combined and dried over calcium chloride, and the chloroform is stripped to yield 41.3 grams of a viscous liquid. Upon distillation of this liquid, there is obtained 27.3 grams of N-( l ,l-dimcthyl-3-hydroxybutyl)acrylamidc boiling at l35l40C./l,5mm.

EXAMPLE 7 To a solution of 25 grams of N-( l ,l-dimethyl-3-oxobutyl)metha'crylamide (diacetone methacrylamide) in 225 grams of ethanol is added, with stirring, 4 grams of sodium bobohydride. An exothermic reaction occurs which causes the temperature of the mixture to rise to 50C. The mixture is stirred for 7 hours and filtered. and the ethanol is removed from the filtrate by evaporation. Watcr is added to the residue which is then extracted with chloroform; the chloroform extracts are dried and the chloroform is removed by vacuum distillation. The product, N-( l.l-dimcthyl-3-hydroxybutyl)- methacrylamide, is obtained boiling at 100 1 02C./0,l mm. The yield is 20 grams. or 8771 of the theoretical amount.

THE POLYMERS The N-3-hydroxyalkyl acrylamides are readily polymerized under free-radical or anionic conditions, either alone or with other monomers. The term polymer" as used herein. refers generally to macromolecules containing repeating units of the formula wherein R" are as previously defined, and includes homopolymers, copolymers, terpolymers and other interpolymers.

The free-radical method is generally the most conve nient one for polymerization of the compounds of this invention. Polymerization by this method may be effected in bulk. solution. suspension or emulsion. by contacting the monomer or monomers with a polymerization initiator either in the absence or presence of a diluent at a temperature of about 02()0C. Suitable free-radical initiators include benzoyl peroxide. tertiary butyl hydroperoxide. acetyl peroxide. hydrogen peroxide, azobisisobutyronitrile. persulfate-metabisulfite. chloratesulfite and the like. Solution polymerization may be effected in an organic solvent such as benzene. toluene. cyclohexane. n-hexane. naphtha. tetrahydrofuran. mineral oil or the like; emulsion and suspension 3 ,8 9,8,279 7 8 polymerization are conveniently effected in water or a tri-, and tetraetc., -chlorostyrenes, -bromstyrenes. mixture of water with a hydroxylated organic solvent. tluorostyrenes, methylstyrenes. -et'hylstyre'nes,

Suitable emulsifiers for use in the preparation of emulsion polymers of this invention include cationic materials such as stearyl dimethyl benzyl ammonium chloride; non-ionic materials such as alkyl aryl polyether alcohols and sorbitan mono-oleate; anionic materials such as sodium decylbenzene sulfonate. dioctyl sodium sulfosuccinate, sodium salts of alkyl arylpolyether sulfates, and sodium lauryl sulfate; alkali metal salts of lignosulfonic acids, silicic acids and the like; and colloidal materials such as casein, sodium polyacrylate, carboxymethyleellulose, Y hydroxyethylcellulose, gum tragacanth, sodium alginate, gelatin. methylcellulose, gum arabic, dextrins or polyvinyl alcohol. Depending on the use to which the polymer is to be put, a particular emulsifier may be preferred; for example, polyvinyl alcohol is incompatible with borax and so some other emulsifier should be used when the polymer is intended as a constituent for a paint to be applied to drywall or the like, which contains borated dextrin.

The compounds of this invention may also be polymerized under anionic conditions using an initiator such as butyllithium or naphthylsodium in tetrahydrofuran. or sodium metal in liquid ammonia.

A large variety of monomers can be used to form interpolymers with-the N-3-hydroxyalkyl acrylamides of this invention. For the most part, these monomers are polymerizable vinyl compounds. They include (1) esters of unsaturated alcohols, (2) esters of unsaturated acids, (3) esters of unsaturated polyhydric alcohols (e.g., butenediol), (4) vinyl cyclic compounds, (5) unsaturated ethers, (6) unsaturated ketones. (7) unsaturated amides, (8) unsaturated aliphatic hydrocarbons, (9) vinyl halides. l0) unsaturated acids, (1 l) unsaturated acid anhydrides, l2) unsaturated acid chlorides, and (13) unsaturated nitriles. Specific illustrations of such compounds are:

l. Esters of unsaturated alcohols: Ally]. methallyl, crotyl, l-chloroallyl, 2-chlor0allyl, cinnamyl, vinyl, methylvinyl, l-phenallyl, butenyl esters of (a) saturated acids such as acetic. propionic, butyric. valeric. caproic and stearic; (b) unsaturated acids such as acrylic, alpha-substituted acrylic (including alkylacrylic, e.g., methacrylic, ethylacrylic, propylacrylic. etc., and arylacrylic such as phenylacrylic), crotonic, oleic, linoleic and linolenic; (c) polybasic acids such as oxalic. malonic, succinic, glutaric, adipic, pimelic, suberic. azelaic and sebaeic; (d) unsaturated polybasic acids such as maleic. fumaric, citraconic. mesaconic. itaconic, methylenemalonic, acetylenedicarboxylic and aconitic; (e) aromatic acids. e.g., benzoic. phenylacetic.

'phthalic. terephthalic and benzoylphthalic acids.

2. Esters of saturated alcohols, such as methyl. ethyl. propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl. Z-ethylhexyl, cyclohexyl or bchcnyl alcohols, with unsaturated aliphatic monobasic and polybasic acids. ex-

amples of which are illustrated above.

3. Esters of unsaturated polyhydric alcohols. e.g., butenediol. with saturated and unsaturated aliphatic and aromatic. monobasic and polybasic acids. illustrative examples of which appear above.

4. Vinyl cyclic compounds including (a) monovinyl aromatic hydrocarbons. e.g., allylbenzenc. styrene, o-, m-, p-chlorostyrenes. -bromostyrenes. -fluorostyrenes.' -methylstyrenes. -ethylstyrenes.

-cyanostyrenes; di-'.'

'-cy anostyren'es; 'vinylnaphthalene, vinylc'yclohexane;

(b) corresponding polyvinyl compounds such as divinylbenzene and trivinylbenzene; and (c) heterocycles such vinylfuran, vinylpyridine, vinylbenzofuran, N- vinylcarbazole. N-vinylpyrrolidoneand N- vinyloxazolidone.

5. Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether. cyclohexyl vinyl ether. octyl vinyl ether, diallyl ether, ethyl methallyl ether and allyl ethyl ether.

6. Unsaturated ketones, e.g., methyl vinyl ketone and ethyl vinyl ketone. i

7. Unsaturated amides, such as acrylamide. methacrylamide, N-methylacrylamide, N-phenylacrylamide, N-allylacrylamide, N-methylolacrylamide. diacetonc acrylamide and N-allylcaprolactam.

8. Unsaturated aliphatic hydrocarbons, for instance, ethylene, propylene. butenes, butadiene, isoprene, 2- chlorobutadiene and alpha-olefins in general.

9. Vinyl halides, e.g., vinyl fluoride. vinyl chloride. vinyl bromide. vinylidene chloride. vinylidene bromide, allyl chloride and allyl bromide.

l0. Unsaturated acids (for example. acrylic, methacrylic, propylaerylic), examples of which appear above.

1 l. Unsaturated acid anhydrides. e.g., maleic. citraconic, itaconic, cis-4-cyclohexene-1,2-dicarboxylic and bicyclo( 2,2,] )-5-heptene-2.3-dicarboxylic anhydrides.

l2. Unsaturated acid halides such as cinnamoyl. acrylyl, methacrylyl, crotonyl, oleyl and fumaryl chlorides or bromides.

l3. Unsaturated nitriles. e.g., acrylonitrile. methacrylonitrile and other substituted acrylonitriles.

The relative proportions of the N-3-hydroxyalkyl acrylamides and the comonomers to be used in interpolymerization depend upon the reactivity of these monomers as well as the properties desired for the interpolymers being formed. To illustrate. interpolymers in which rigidity is desired are obtained by polymerization of a mixture of monomers having a few substitutions or substitutions of relatively short chain length. If a still higher degree of rigidity is desired, a monomer mixture may be used in which a small amount of a bifunctional monomer is included such as divinylbenzene which will crosslink the polymer. On the other hand. interpolymers having a high degree of solubility in a hydrocarbon oil are obtained from a polymerization mixture containing a relatively high proportion of an oilsolubilizing monomer. i.e., one having an aliphatic group containing at least about 8 carbon atoms. For most applications, it has been found that the oilsolubilizing monomer should comprise at least about 50% (by weight). preferably at least about of the interpolymer. I

Polymers according to this invention may also be prepared by the reduction of polymers of N-3- oxohydrocarbon-substitutcd acrylamides. The reduction method may be any one which will reduce the carbonyl group; the use of sodium borohydride or hydrogenation in the presence of a hydrogenation catalyst such as Raney nickel are preferred. When a diacetone acrylamide homopolymer isthus reduced. the product may a homopolymer of N-( l.l-dimethyl- 3-hydroxybutyUa Cryl'aniide or a copolymer with 'diacetone 9 acrylamide, depending on the degree of completion of the reduction. 7

The preparation of polymers of this invention is illustrated by the following examples.

EXAMPLE 8 A solution of 2 grams of sodium borohydride in 50 ml. of methanol is added dropwise, over 10 minutes, to a solution of grams of a diacetone acrylamide polymer in 350 ml. of methanol. The reaction is exothermic and the temperature rises to about 40C. The mixture is heated under reflux for two hours and then cooled, after which another gram of sodium borohydride is added and refluxing is continued for 2 hours. Acetic acid is added to neutralize the mixture, which is then filtered and added dropwise to 5 liters of water. The N- l ,l-dimethyl-3-hydroxybutyl )acrylamide polymer precipitates and is removed by filtration and dried in air for 3 days.

EXAMPLE 9 1 EXAMPLE 10 By the method of Example 8, grams of a copolymer of 7371 diacetone acrylamide and 27% ethyl acrylate is reduced with 2 grams of sodium borohydride. The reaction is carried out in solution in 650 ml. of ethanol. The product is a copolymer of N-( 1,1-dimethy1-3- hydroxybutyhacrylamide and ethyl acrylate.

EXAMPLE 1 1 A copolymer of equal amounts of diacetone acrylamide and diacetonc methacrylamide is prepared in aqueous emulsion; using an ammonium persulfate-sodium metabisulfitecatalyst and an oxyethylated alkylbenzene dispersing agent. To a solution of 45 grams of this copolymer in 500 ml. of ethanol is added a'suspension of 4.9 grams of sodium borohydride in 100 ml. of ethanol. The reaction mixture is allowed to stand overnight and is then acidified with glacial acetic acid 'to a pH of 7. The resulting copolymer is precipitated by pouring into a tenfold excess of water and is -the n'dried.

EXAMPLE 12 Following the procedure of Example 1 1. a polymer is prepared by sodium borohydride reduction of a 60:40 copolymer of diacetone acrylamide and diacetone methacrylamide.

EXAMPLE 13 A solution of 100 grams of N-( 1,1-dimethyl-3- hydroxyhutyl)aerylamide in 400 grams of benzene is heated to reflux and purged with nitrogen. after which a solution of 2 grams of azobisisobutyronitrile in 40 ml. of benzene is added. The polymerization reaction begins immediately. and the mixture is stirred and cooled to room temperature. The orange gel-like homopolymer is agitated with heptane ,and dried in a vacuum oven. It is then purified by dissolving in 2.5 liters of methanol and reprecipitating from 7 liters of water.

The purified polymer is removed by filtration and airdried.

EXAMPLE 14 A solution Of 200 grams of N-(1,1-dimethy1 3- hydroxybutyhacrylamide, 2 grams of ammonium persulfate and 2 grams of sodium metabisulfite in 2000 grams of distilled water is agitated for one hour, during which time the desired homopolymer precipitates. It is removed by filtration, washed with water and dried in a vacuum oven at 58C.

EXAMPLE 15 A solution of 10 grams of N -(1,1-dimethyl-3-hydroxybutyl )acrylamide, 0.1 gram of sodium lauryl sulfate and 0.2 gram each of ammonium persulfate and sodium metabisulfite in 90 grams of water is heated to 60C. with stirring for three hours. Polymerization occurs and an aqueous latex is formed. The latex can be broken by the addition of a few drops of 10% aqueous hydrochloric acid, whereupon the polymer precipitates and may be collected by filtration.

EX MPLE 16 A solution of grams of vinyl acetate in 386 ml. of benzene is heated to 79C., and a solution of 2.5 grams of azobisisobutyronitrile in 50 ml. of benzene is added. After the mixture has been heated for 35 minutes, a solution of 10 grams of N-( l,1-dimethyl-3-hydroxybutyl- )acrylamide in 57 ml. of benzene is added dropwise over 1 hour. Stirring and heating is continued for one hour, after which time ml. of methanol is added and the mixture is cooled. The 1:9 copolymer of N- 1, l -dimethyl-3-hydroxybutyl )acrylamide and vinyl acetate is precipitated by adding to 6 liters of textile spirits, dissolved in ethanol and reprecipitated by the addition of water. An emulsion is formed when the water is added; this emulsion is broken by the addition of 100 grams of sodium chloride and 20 ml. of hydrochloric acid. After an additional precipitation from aqueous ethanol. the copolymer is dried in a vacuum oven at 60C.

crylamide, 2 grams of azobisisobutyronitrile and 400 ml. of benzene.

EXAMPLE 18 Following the procedure of Example 16, a 3:1 copolymer of N-( 1 ,1-dimethyl-3-hydroxybutyl )aerylamide and vinyl acetate is prepared from 25 grams of vinyl acetate, 75 grams of N-(1,1-dimethyl-3-hydroxybutyl)acrylamide, 0.2 gram of azobisisobutyronitrile and 400 grams of benzene.

EXAMPLE 19 Following the procedure of Example 16. a 9:1 copolymer of N-( l.l-dimethyl-3-hydroxybutyl)acrylamide and vinyl acetate is prepared from 5 grams of vinyl acetatc, 45 grams of N-(1.1-dimethyl-3-hydrox- 1 l ybutyl)acrylamide. 0.2 gram of azobisisobutyronitrile and 400 grams of benzene.

EXAMPLE 20 A solution of grams of N-( l,l.-dimethyl-3-hydroxybutyl)acrylamide, 45 grams of vinyl acetate, 0.5 gram of ammonium persulfate and 0.5 gram of sodium metabisulfite in 200 grams of water is stirred at room temperature for one hour. The polymerization reaction is then quenched by the addition of hydroquinone. The polymer emulsion which is formed is broken by freezing and the desired 1:9 copolymer of N-( 1.1-dimethyl- 3-hydroxybutyl)acrylamide and vinyl acetate is removed by filtration and dried in a vacuum oven.

EXAMPLE 21 Following the procedure of Example 20. a 1:1 copolymer of N-( l ,1-dimethyl-3-hydroxybutyl)acrylamide and vinyl acetate is prepared from grams of each of the monomers, 0.2 grams each of ammonium persulfate and sodium metabisulfite and 80 grams of water.

EXAMPLE 22 EXAMPLE 23 A mixture of grams of N-( 1.1-dimethyl-3-hydroxybutyl)acrylamide. 5 grams of ethyl acrylatc, 0.5 gram each of sodium metabisulfite and ammonium persulfate and 200 grams of water is stirred at room temperature for /z hour. The desired 9:] copolymer of N-( 1,1- dimethyl-3-hydroxybutyl)acrylamide and ethyl acrylate precipitates and is removed by filtration and dried in a vacuum oven.

EXAMPLE 24 A mixture of 5 grams of ethyl acrylate. 0.25 gram of sodium lauryl sulfate and 400 grams of water is heated to 60C. and a solution of 0.25 gram of ammonium persulfate in 5 ml. of water is added. After polymerization has proceeded for one-half hour, a solution of 45 grams of N-(1.1-dimethyl-3-hydroxybutyl)acrylamide in 45 grams of water is added over l5-minutcs. The mixture is heated at 60C. and stirred for an additional two hours; a latex is formed which breaks at the end of this time to yield the desired 9:l copolymer of N-( 1.1- dimethyl-3-hydroxybutyl)aerylamide and ethyl acrylate. This polymer is filtered. washed with water and dried in a vacuum oven.

EXAMPLE 25 A solution of 37.5 grams of N-( 1.1-dimethyl-3- hydroxybutyl)acrylamide and 12.5 grams of styrene in 950 grams of benzene is heated to reflux and 0.5 gram of azobisisobutyronitrile is added. Refluxing is continucd for seven hours as the desired 3:1 copolymer of N- (l.l-dimethyl-3-hydroxybutyl)acrylamide and styrene 1 2 is formed. The'benzene solution is cooled and poured into heptane. whereupon the copolymer precipitates and is collected by filtration and dried.

EXAMPLE 26 Following the procedure of Example 25, a 1:1 copolymer of N-( l.1-dimethy1-3 hydroxybutyl)aerylamide and styrene is prepared.

EXAMPLE .2?

A solution of 37.5 grams of N-( l.l-dimethyl-3- hydroxybutyl)acrylamide, 12.5 grams of acrylic acid and 0.5 gram each of ammonium persulfate and sodium bisulfitc in 200 grams of water is stirred at room temperature for about /2 hour. The 3:] copolymer of N- l,l-dimethyl-3-hydroxybutyl)acrylamide and acrylic acid is removed by decantation; the polymer is cut into small pieces, washed with water and dried in a vacuum oven.

EXAMPLE 28 A solution of 47.5 grams of N-( 1,1-dimethyl-3- hydroxybutyl)acrylamide and 2.5 grams of glycidyl methaerylate in 500 grams of benzene is heated to 50C. and 0.05 gram of azobisisobutyronitrile is added. Polymer formation is evidenced by the formation of a gel within 4 hours. The gel is dissolved in acetone and precipitated by the addition of water; the precipitate. which is the desired 19:1 copolymer of N-( 1.1- dimethyl3-hydroxybutyl)acrylamide and glycidyl methaerylate. is dried in a vacuum oven.

EXAMPLE 29 lsohutyraldehyde. 144 grams (2 moles). is added at 20C. to a solution of 160 grams (2 moles) of sulfur trioxidc in 352 grams of dioxane and 750 ml. of ethylene dichloride. The reaction mixture is allowed to warm to room temperature and stirred for one hour. after which 2190 grams (30 moles) of acrylonitrile and 294 grams (3 moles) of sulfuric acid are added. An exothermic reaction occurs and the temperature of the reaction mixture is maintained at 40C. until the reaction is complete. The mixture is then cooled to 0C. and treated with sufficient anhydrous ammonia to neutralize the sulfonic acid formed. Upon dilution with ethylene dichloride. the ammonium salt of 1.1- bis(acrylamido)-2-methylpropane-2-sulfonic acid is precipitated. The solid product is filtered and dissolved in methanol: the methanol solution is filtered and the methanol is removed by evaporation. The purified salt is washed with acetone and ether and dried in a vacuum oven.

A solution of 2 grams of the acrylamidosulfonate. 18 grams of N-(1.l-dimethyl-3-hydroxybutyl)acrylamide and 0.005 gram of azobisisobutyronitrile in grams of methanol is heated to reflux for 2 hours. whereupon a yellowish gel forms. This gel. the desired 9:] copolymer of N-(1.l-dimcthyl-3-hydroxybutyl)acrylamide and ammonium l .1-bis(acrylamido)-2-methylpropane-2- sulfonatc, is washed with acetone in a Waring blender and dried in a vacuum oven.

The polymers of this invention have a wide variety of uses. A property of N-3-hydroxyalkyl acrylamide polymers which contributes to the diversity of their uses is breathability;" that is, their high porosity to water vapor and gas. This property is accompanied. however. by resistance to chemical and physical attack. 0

The polymers may be combined with pigments, fillers, dyes, extenders, emulsifiers and solvents of various kinds to form inks. paints and the like; or they may be used to increase the gloss of commercial semi-gloss paints such as alkyd paints. Many of the polymers, when prepared in latex form, serve as thickencrs for water systems, including water-base paints.

The polymers may be formulated into thermoplastic or pressure-sensitive adhesives, depending on whether it contains relatively little or a larger amount, respectively, of a plasticizer or plasticizing comonomer.

Powders suitable for molding and coating formation may be obtained by precipitation or spray-drying of the polymers of this invention. especially from latices. For this purpose, it is preferred that the soap or emulsifier content of the latex be kept very low.

Oil-soluble polymers of this invention, especially copolymers containing at least about 50% by weight of units derived from an oil-solubilizing comonomer such as an alkyl acrylatc having at least about eight carbon atoms, improve the viscosity properties of lubricants. Other uses include fiber formation; protective coatings for photographs. preserved plants. etc.; soil binders for airplane landing strips; sizing compositions for fiberglass mat formation; preparation of sheeting for waterrepellent garments and coverings such upholstery and raincoats; produce wrap for foods requiring a semipermeable package; treatment of leather in shoes. gloves and the like; and formation of magnetic recording tapes by suspension of iron oxide in a latex and formation of a film thereof on a polyester or cellulose acctatc backing.

FILMS Many of the uses of N-3-hydroxyalkyl acrylamide polymers involve the preparation of films or sheets therefrom. (The terms film" and sheet," as used in the polymer art. respectively denote fabrications having a thickness of up to mils and greater than 10 mils; for the sake of brevity. the use of the word film" hereinafter will include both films and sheets.) The preparation of films may be accomplished by simply applying a latex of the polymer to a surface (e.g., by brushing, roller-coating or dip-coating) and allowing it to dry. Films amy also be prepared from bulk, solution, suspension or emulsion polymers; the preparation of such films is often conveniently effected by dissolving the polymer in a suitable solvent and casting on a flat surface.

The casting solvent for film formation may be any organic liquid which dissolves the polymer and which may itself be easily removed when the film has been formed. Suitable solvents include aliphatic alcohols, ketoncs, ethers. esters and the like: aromatic hydrocarbons such as benzene. toluene and Xylene; and halogenated aromatic compounds such as chlorobenzcne or o-chlorotoluene.

The polymer film is prepared by casting the polymer solution on a suitable surface such as glass or cellophane. the thickness of the solution being on the order of 1-5 mils, and allowing the solvent to evaporate. In some cases. eurporation ofthe solvent may be aided by gentle heating. The film is then released from the casting surface by a suitable method, typically by immersing the surface and film in water.

Films and sheets of the polymers of this invention may also be prepared by extrusion, injection molding or similar methods; these are frequently more suitable than casting for producing such films commercially.

it is frequently advantageous to incorporate an auxiliary swelling agent in the casting solution. A film prepared from such a solution containing an auxiliary swelling agent often possesses improved properties as a desalination membrane, as hereinafter described. Particularly useful swelling agents for this purpose include perchlorates, especially magnesium perchlorate, and lower molecular weight amides such as formamide. dimethylformamide and a'cetamide.

The properties of the films may often also be improved by heating them at about 50l 50C., at atmospheric or elevated pressures.

The preparation of films from the polymers of this invention is illustrated by the following examples.

EXAMPLE 30 A solution of 7 grams of the N-( l ,l-dimethyl-3- hydroxybutyl)acrylamide homopolymer of Example 15 in 100 grams of methyl ethyl ketone is cast on a glass plate. The film is allowed to dry overnight to form a 0.7-mil film which is heated at 7()-75C., for one hour and soaked in water for 2 hours, after which time it is removed from the glass plate.

EXAMPLE 3 l A solutionof 10 grams of the copolymer of Example 10 in 45 grams each of methyl ethyl ketone and dimethylformamide is cast on a glasssurface and allowed to dry. The film thus formed 1 mil) is heated and soaked in water as described in Example 26, and is then removed from the glass plate.

EXAMPLE 32 A solution of 15 grams of the N-(l,l-dimethyl-3- hydroxybutyl)acrylamide-vinyl acetate copolymer of Example 18 in 85 grams of acetone is cast on a glass plate and allowed to dry. The resulting film is heated and soaked in water as described in Example 26. The final film thickness is 1 mil.

EXAMPLE 33 A solution of 20 grams of the N-( l,l-dimethyl-3- hydroxybutyl)aerylamide homopolymer of Example 1 3 and 0.2 gram of magnesium perchlorate in 2 grams of water and grams of acetone is cast on a glass plate and allowed to dry to form a l.l-mil film. This film is released from the glass plate by soaking in water and is then heated at 60C. for 15 minutes.

EXAMPLE 34 A solution of 20 grams of the homopolymer of Example l3 in 30 grams of formamide and 80 grams of acetone is cast on a glass plate and dried to form a l.5-mil film. The film is released by soaking in water and is then heated for 15 minutes at 40C.

CROSSLINKED POLY MERS Polymers of the N-3-hydroxyalkyl acrylamides of this invention may be crosslinked to form polymeric compositions with increased strength, rigidity and resistance to chemical attack.

Two types of crosslinking agents may be used to form the crosslinked polymers of this invention. The first type reacts with the polymer to induce mutually reactive sites on the polymer molecule, thereby causing the on the polymer chain itself. or ,onuthe substituent groups. If they are on the chain, they are mostconve- 16 and other properties of the films. It is believed that, in addition to esterifying the alcoholic hydroxyl groups, these acid halidescause dehydrative cyclization of the pendant chains on the. polymer molecule to form an oxniently formed by a-free radical catalyst and consist of 5 azine moiety as follows [using an N-(l,1-dimethyl-3- 'free radicals which mayreact with each other as dehydroxy u yl)a ryl rni e polymer fl 'illuStrated].

H-CH. -Cll-----CH;;-

RCOCI c=o RCOOH HCl N-H O N ca -c-ca, T

(:HOH CH3 I G scribed. if the sites are on the substituent groups, they 20 The same reaction occurs when. the polymer is treated may be formed by any reagent which will create on the substituent a moiety capable of reacting with a similar moiety or with another one which is present in the molecule. ln general, the term mutually reactive site" denotes a potential point where at least two polymer molecules can be connected by a valence bond which does not involve atoms extraneous to the polymer being crosslinked.

The second type of crosslinking agent reacts with a plurality of polymer molecules to form a molecular bridge between them. By molecular bridge is meant a linkage containing at least one atom extraneous to the polymer itself. The molecular bridge may be organic or inorganic and may be attached to the polymer chain or the substituent, more often the latter.

It will be apparent that the variety of reagents which can be used for crosslinking, especially of the second type described above, is very wide; it includes, in a broad sense, any compound having at least two functional groups which react with an active site on the polymer molecule, usually the hydroxy radical. The preferred classes of compounds of this type are polyisocyanates, aldehydes (in acid medium), oxidizing agents and polycarboxylic acid derivatives. Also useful for crosslinking copolymers containing acidic groups (e.g., acrylic acid-containing interpolymers) are polyvalent metal salts or oxides.

Oxidizing agents are believed to function by oxidizing the terminal methyl group to a carboxylic acid group which may then form a salt with the oxidizing agent or its reduction product. The oxidizing agent may also serve as a crosslinkcr of the first type by forming an acid, which in turn condenses with another acid group to form an anhydridc. Chromium trioxide is the preferred oxidizing agent, but other suitable oxidizers include potassium permanganate and potassium perchlorate.

Polyisocyanates react with the hydroxy groups of two (or more) polymer molecules to form a polyfunctional urethane bridge. Polycarboxylic acid derivatives (preferably the acid halides or anhydridesj similarly react to form a polyfunctional ester bridge. Typical crosslinking agents of these types include toluene diisocyanate. succiniyl chloride, succinic anhydride, glutaryl chloride and adipyl chloride. Treatment of the polymers with monocarboxylicacid halides also results in modification which, in certain instances. improves desalination LII with other dehydrating agents such as phosgene, sulfuric acid, alumina, phosphorus pentoxide and the like. Aldchydes (preferably formaldehyde) react. in acid solution, with the hydroxy groups of two polymer molecules to form an acetal bridge.

The use of polyvalent metal salts or oxides for crosslinking is often advantageous when the polymer contains acidic units, such as those derived from acrylic acid. The reaction of the metal oxide or salt with the polymer may be one of neutralization of the acidic groups, or one of double decomposition of a salt thereof.

Of the crosslinking agents of the first type, the preferred species are the free radical catalysts. These include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile and the like. They are believed to function by creating free radical sites on the polymer chain, thereby causing condensation to form a crosslinked structure.

I The crosslinking methods described hereinabove may be used on the polymers themselves, in bulk or in particulate form. Most often, however, they are useful for treatment of polymer films. For this purpose, a film of the desired polymer is treated with a crosslinking agent, optionally in a solvent or diluent, at a temperature at which reaction occurs (ordinarily from room temperature up to about C).

Films, ,both simple and crosslinked, of N-3- hydroxyalkyl acrylamide polymers have excellent tensile strength and elongation properties. They may be used, as oil-resistant coatings on paper, as breathable protective coatings on fabrics. or as protective coatings on woods such as plywood.

The preparation of crosslinked and otherwise posttreated polymers and polymer films of this invention is illustrated by the following examples.

-' hour. The film is then soaked in a 10% solution of tolu- 'ene' diisocyanate in xylene for -l hour. rinsed with xylene and blotted dry. The crosslinked film is soaked in water for; 48 hours and removed from the glass plate.

EXAMPLE 36 The N-( l l -dimethyl-3-hydroxybutyl )acrylamideethyl acrylate copolymer of Example 24 is dissolved in a mixture of dimethylformamide and acetone and a film thereof is cast on glass. Following a procedure similar to that of Example 35, an 0.5-mil toluene diisocyanate-crosslinked film is prepared by treating the film with a 2.5% solution of toluene diisocyanate in xylene.

EXAMPLE 37 A film of an N-( l,1-dimethyl-3-hydroxybutyl)acrylamidevinyl acetate copolymer is prepared from the casting solution described in Example 32, dried 30 minutes and soaked for 45 minutes at 50C. in a solution of 300 ml. of 37% aqueous formaldehyde and 100 ml. of sulfuric acid in 1 liter of water. The crosslinked film is then soaked in water for minutes, released from the glass surface and heated between two chrome plates to 80C. under 2000 psig. pressure for 45 minutes. The final film thickness is 1 mil.

EXAMPLE 38 Following the procedure of Example 37, a film of the N-( l. l -dimethyl-hydroxybutyl )acrylamide-vinyl acctate copolymer of Example 19 is cast on glass. The film is dried for A: hour, heated at 75C. for 1 hour and released by soaking in warm water. It is then submerged in a solution of 100 ml. of 37% aqueous formaldehyde and 10 ml. of sulfuric acid in 100 ml. of distilled water, at 50C. for 1 hour. The crosslinked film (0.9 mil) is rinsed for /2 hour in water.

EXAMPLE 39 To a solution of 25 grams of the N-(l,1-dimethyl-3- hydroxybutyl)acrylamide-vinyl acetate copolymer of Example 19 in 75 grams of acetone are added grams of dimethylformamide and 0.25 gram of adipyl chloride. The solution is shaken for 1 hour, allowed to stand for 15 minutes and cast on glass. The film is allowed to dry for 10 minutes, soaked in water for 2 /2 days to release from the glass surface and then heated at 50C. for 15 minutes.

EXAMPLE 40 Following the procedure of Example 39, 30 grams of the N-( l .1-dimethyl-3-hydroxybutyl)acrylamide homopolymer of Example 14 is dissolved in 170 grams of acetone and 40 grams of dimethylformamide and is crosslinked with 0.3 gram 1% of polymer weight) of adipyl chloride. A film of the crosslinked polymer is then cast on glass.

EXAMPLE 41 EXAMPLE 43 A solution of 20 grams of the polymer of Example 1 l and 2 grams of adipyl chloride in grams of acetone and 16 grams of dimethylformamide is heated for 2 hours at 65-70C. and allowed to cool to room temperature. A IO-mil film of the product is cast on glass, dried for 3 minutes, immersed in water for 15 minutes at 6065C. and removed from the glass surface.

EXAMPLE 44 Following the procedure of Example 43, a crosslinked film is prepared from 20 grams-of the polymer of Example 1 l, 3 grams of adipyl chloride, 80 grams of acetone and 8 grams of dimethylformamide.

EXAMPLE 45 Follwoing the procedure of Example 43, a crosslinked film is prepared from 20 grams of the polymer of Example 12, 1 gram of adipyl chloride, grams of acetone and 20 grams of dimethylformamide.

EXAMPLE 46 To a solution of 17.1 grams of the homopolymer of Example 14 and 7.9 grams of pyridine in 132 grams of acetone is added dropwise 11.8 grams of acetyl chloride. The mixture is stirred for 2 hours, and then the pyridine hydrochloride which forms is removed by filtration and the post-treated polymer is recovered by pouring the acetone solution into heptane. The polymer is washed with an aqueous sodium bicarbonate solution and'dried in a vacuum oven.

EXAMPLE 47 Succinyl chloride, 5 grams, is added dropwise to a solution of 8.55 grams of the homopolymer of Example 14 and 2 grams of pyridine in 60 grams of acetone. The mixture is stirred for 2 hours, whereupon it forms a gel. Stirring of the gel is continued for slightly more than one hour, and the mixture is then allowed to stand for 2% days whereupon a white solid separates by precipitation. The mixture is filtered and the solid, crosslinked polymer is washed with an aqueous solution of sodium bicarbonate and dried in a vacuum oven.

EXAMPLE 48 Following the procedure of Example 46, 8.55 grams of the homopolymer of Example 14 is crosslinked with 5.1 grams of phthalyl chloride in 64 grams of acetone and 2 grams of pyridine.

EXAMPLE 49 Following the procedure of Example 46, 8.55 grams of the homopolymer of Example 14 is dissolved in 70 grams of acetone and 4 grams of pyridine and is crosslinked with 5.2 grams of isophthalyl chloride.

EXAMPLE 50 Glutaryl chloride, 4.2 grams. is added dropwise to a solution of 8.55 grams of the homopolymer of Example 14 in 61 grams of acetoneand 4 grams of pyridine. The reaction mixture forms a gel in 30 seconds; the gel is washed with aqueous sodium bicarbonate solution and agitated with hcptane in a blender. The polymer is removed by filtration and dried.

EXAMPLE 51 To a solution of 8.55 grams of the homopolymer of Example l4 in 60 grams of acetone is added dropwise 3.2 grams of oxalyl chloride. The reaction mixture forms a gel in 30 seconds; the gel is washed with aqueous sodium bicarbonate and agitated with heptane in a blender. The polymer is removed by filtration and dried at 50C. in a vacuum oven.

EXAMPLE 52 Following the procedure of Example 5 l 8.55 grams of the homopolymer of Example 14 is erosslinked with 3.5 grams of malonyl chloride.

DESALINATION OF WATER General mention has been made of the high water vapor and gas transmission rates of the polymers of this invention. Accordingly, these polymers are useful wherever a breathable" or semi-permeable film is desirable. Typical applications include formation of membranes for use in equipment designed to supplement bodily functions, such as artificial kidneys; in purification of chemical products, both aqueous and nonaqueous; and in removal of dissolved impurities, especially salt, from water by hyperfiltration.

The problem of removal of dissolved impurities from water, especially conversion of saline water into potable water, is currently a subject of great interest. Consumption of fresh water in metropolitan areas is often so high that existing water supplies are insufficient to meet the demand. Water shortages of varying degrees of severity have resulted in several parts of the country. In view of the dwindling sources of fresh water and the vast supply of sea water and brackish water which has so far been unusable, the potential importance of methods for desalinating such water is obvious.

Some of the methods which have been proposed for desalination are distillation, crystallization, solvent extraction, ion exchange, electrodialysis, and hyperfiltration or reverse osmosis. The last of these is of great interest because it is potentially the most efficient and economical way of accomplishing desalination. Basically, the process is one in which water containing dissolved impurities is forced under pressure through a membrane which generally passes water more readily than it passes the impurities. It differs from electrodialysis, the other important membrane method, in that water is removed from salt rather than salt from water and that the driving force is pressure rather than electrical potential.

In the present specification, the term hyperfiltration" is used to refer to any process in which low molecular weight solutes, which are generally inorganic but may include certain organic molecules and also bacteria or viruses in certain instances, are removed from water under pressure by passage through a membrane. The term reverse osmosis" is often applied to this process because of the commonly held belief that to effect flow of water through the membrane at least enough pressure must be exerted to overcome the osmotic pressure of the solution. This view is not actually correct since all that is really necessary is to overcome the difference between the osmotic pressures of the feed and product solutions.

The following terms are frequently used in discussionsof the hyperfiltration process.-

Flux is the quantity of a substance passing through a surface of unit area during unit time. IN particular,

water flux is the amount of water which passes through a surface, such as a membrane, of unit area during unit time.

Salt rejection" is the amount of the salt rejected by a desalination membrane, and is defined as the difference between the salt concentration of the influent and that of the effluent divided by the salt concentration of the influent.

Water vapor transmission rate" is the amount of water passing through a membrane of unit area and unit thickness within a given time. It has been found that there is a direct correlation between water'vapor transmission rate and the solubility of water in the membrane, and hence between transmission rate and the ability of the membrane to function in the hyperfiltration process.

Three properties are essential for a good desalination membrane. First, the polymer comprising the membrane must be hydrophilic. Second, the membrane must have sites for hydrogen bonding. Third, the membrane must exhibit a high permeability of water relative to salt. A fourth property previously considered necessary was a erosslinked or highly crystalline structure in the membrane; however, it has been discovered that membranes prepared from the polymers of this invention need not be chemically erosslinked, although such crosslinking is often desirable.

The polymeric substance which has heretofore been most widely used for the preparation of membranes for desalination by hyperfiltration is cellulose acetate. Films of cellulose acetate are highly hydrophilic and capable of forming hydrogen bonds, but they suffer from a number of disadvantages. First, they are low in strength and durability, especially when in contact with solutions high in salt. Second, they require special processing to be usable as desalination membranes. Third, they must be kept continuously in contact with water after processing.

Membranes of the N-3-hydroxyalkyl acrylamide polymers of this invention are free of these disadvantages. Moreover, they have high water fluxes and salt rejections; this is especially true of membranes prepared from erosslinked polymers.

Several interesting structural correlations with desalination effectiveness ofthe N-3-hydroxyalkyl acrylamide polymers have been discovered. in the first place, copolymers with oxygen-containing monomers are particularly effective; these oxygen-containing monomers include ethers such as ethyl vinyl ether and methyl 2- butenyl ether, kctones such as methyl vinyl ketone and methyl allyl ketone, and esters such as ethyl acrylate, ethyl methacrylate, vinyl acetate and diethyl maleate. Especially useful are copolymers of N-( l.l-dimethyl-3- hydroxybutyl)acrylamide and its methacrylamide homolog. C opolymers containing about 5-407: (based on total monomer weight) of a polymerizable ester, especially a low alkyl acrylate or a vinyl carboxylate. are also suitable. I

In the second place. polymers which exhibit a high degree of short-range ordering when examined by X-ray diffraction form particularly good desalination membranes. In general, copolyiners of N-3- hydroxyalkyl acrylamides with nitrogenand oxygencontaining monomers show higher short-range ordering than homopolymers; these copolymers include the ones with nitriles such as-acrylonitrile and the oxygencontaining ones previously described.

The essential features of a hyperfiltration desalination unit include a pressure cell or vessel for containing membrane, such as cellulose acetate, a low circulation rate such as is provided by convection is sufficient. However, when the water flux is high, a boundary layer of solution of very high salt content is formed at the the feed (water to be desalinated). circulation means membrane and this may result in low salt rejection unfor contacting this water with the membrane,. and less the flow of water past the membrane remains turmeans for removing the product (desalinated water) on bulent so that the boundary layer is diluted. the ppp slde f the T f A y i unit is The effectiveness of the desalination method of this w" m the drawmgs m whlch l 15 a Cross invention is shown by a test in which an aqueous solusectional view of the entire desalination apparatus and tion f Sodium chloride Content (corresponding 2 is a detail of the membrane housing and assem' to brackish water) was desalinated in an apparatus simyilar to that shown in the drawing. The membranes used The apparatus conslst? of an flutoclave or slmllar in the respective tests were each 2 inches in diameter Pressure Vessel 1, fitted Wlth a gas Inlet a P a gas and were prepared from the polymeric .films ofthis in- Valve and dram Valve The gas Inlet 2 vention. The tests were run at room temperature and tached to a cylinder or other gas source and carries a at a pressure f6 15()() psig. ci m ti f thg l Pressum gauge 6 and a blowout or Safety Valve tion was effected by a circulating pumppSamples of the The autoclave l is connected by conduits 8 and 9, the product were taken periodically and tested for salt conlatter being fitted with a pump 10 or equivalent cir'eulatent, and salt rejection was calculated therefrom. The tion means, to membrane housing 1 1. This housing table gives the pressure and time elapsed in the run,.the consists of two solid housing units l2 and 13, fastened maximum salt rejection for each of the membranes together when in use by a plurality of bolts 14 (of which tested, the average salt rejection over the entire test only one is shown); two sealing members 15 and 16, and the approximate water flux.

Water flux Salt rejection,% Pressure, (approx. Membrane psig. Time gaL/ft /day Maxi- Average .mum

EX. 600 205 min. 6.5 50.7 I 31 600 14 min. 12 96.8 7 .3 32 6004000 50 min. 13 63.0 44.1 33 600 10 min. 1.5 83.5v :34 600 6 min. 2 l6 82.5 62 36 600-1000 11.8 hrs. 17 96.7 89 37 1000 5.2 hrs. 7 82 69.2 38 600-l500 355 min. 2 99 96.5 39 00 28.5 hrs. 15 98.4 95.6 40 600 9.3 hrs. 44 99.4 94.9 41 600 168 hrs. 73 97.5 94.7 42 600 145 min. 110 99.2 96.3

40 I typically rubber Orings, which fit into circular grooves I In a similar test, the membrane of Eitample 35 was 17 and 18 in the housing units, groove 17 forming 21 evaluated at 600 psig., using a 3.5% salt solution. Salt circle of smaller diameter than groove 18 so that the rejection was 80.9% at an average flux of about 3.4 membrane fits snugly against its support: the desalina- 4S gaL/ftF/day. tion membrane 19: and cushioning means 20, typically Tests were run on the membranes of examples 43-45 a piece f filt a Upper hgusing u it 12 ha a at 600 psig., using a 1% salt solution. The following reshallow cylindrical recess 21 with which conduits 8 S were Obtilmedand 9 communicate. Lower housing unit 14 has a conical depression in which a porous conical disk 22 is mounted: this depression terminates in outlet port Water flux s} M b T (alp rox), Salt rejection, (7

The operation of the apparatus may be generally deem mm l (average) scribed as follows: Autoclave l is charged with feed g- 12 4i hrs. n 95.7

. 7 water through port 3, and gas (preferably an inert gas 45 2g; 5g 3%; such as nitrogen. helium or argon) is introduced via inlet 2 until the pressure within autoclave 1 has reached the desired level. The feed is circulated through con- It will be seen from these results that the membranes duit 8, recess 21 and conduit 9 by means of pump l0; prepared by crosslinking, with adipyl chloride, copolyalternatively other means of circulation may be used, mers of N-( l,l-dimethyl-3-hydroxybutyl)acrylamide such as convection which may be effected by cooling with N-(1,l-dimethyl-3-hydroxybutyl)methacrylamide conduit 8 and heating conduit 9. Under the pressure in afford very high salt rejections at high flux. autoclave l,water is desalinated as it is forced through In addition to the films, latices and coatings demembrane [9; the product passes through cushioning scribed hcreinabove, the polymers of N-3-hydroxyalkyl means 20 and porous disk 22 and is collected at outlet (6 acrylamides may be formed by known techniques into port 23.

The velocity at which the water circulates through recess 21 should be adjusted according to the water flux through membrane 19. In the case of a low-flux a wide variety of other articles, including structural units, fibers and the like.

What is claimed is:

l. A compound of the formula wherein R is a hydrocarbon radical; each of R R, R, and R is individually hydrogen or a hydrocarbon radical; and R is hydrogen or a lower alkyl radical.

2. A compound according to claim 1 wherein R, R

- and R are alkyl radicals; R is hydrogen or an alkyl 'radical; R is hydrogen and R is hydrogen or methyl.

3. A compound according to claim 2 wherein R, R and R are lower alkyl radicals; R and R are hydrogen; and R is hydrogen or methyl.

' 4. N-( l ,1-Dimethyl-3-hydroxybutyl)acrylamide, the compound of claim 1 wherein R, R and R are methyl and R R and R are hydrogen.

5. N-( l l -Dimethyl-3-hydroxybutyl )methacrylamide, the compound of claim 1 wherein R, R, R and R are methyl and R and R are hydrogen.

6.'A method for the preparation of a compound according to claim 1 which comprises reducing the carbonyl group of an N-3-oxohydrocarbon-substituted aerylamide of the formula which comprises 1 reducing N-( 1,1-dimethyl-3- oxobutyl)methacrylamide with sodium borohydride.

10. A method for the preparation of a compound according to claim 1 which comprises (1) reacting an alcohol of the formula ROH, wherein R is a lower alkyl radical, with an N-3-oxohydrocarbon-substituted acrylamide of the formula.

in the presence of a strongly alkaline catalyst to form an N-3-oxohydrocarbon-substituted 3-alkoxypropionamide; (2) reducing the keto carbonyl group of said 3-alkoxypropionamide; and (3) removing the alkoxy group to regenerate the olefinic bond.

11. The method of claim 10 wherein step (2) is accomplished by hydrogenation.

12. The method of claim 11 wherein the hydrogenation is effected in the presence of a Raney nickel catalyst.

13. The method of claim 10 wherein step (3) is accomplished by pyrolyzing the 3-alkoxypropionamide in the presence of strong alkali.

14. A method according to claim 10 for the preparation of N-( l,l-dimethyl-3-hydroxybutyl)acrylamide which comprises l reacting N-( l ,l-dimcthyl-3- oxobutyl)acrylamide with methanol in the presence of a strongly alkaline catalyst to form N-( 1,1-dimethyl-3- oxobutyl)-3-methoxypropionamide; (2) reacting said N-( l l -dimethyl-3-oxobutyl )-3-methoxypropionamide with hydrogen in the presence of Raney nickel to form N-( l, l -dimethyl-3-hydroxybutyl )-3-methoxypropionamide; and (3) removing the methoxy group therefrom by pyrolysis at about l50200C. in the presence of UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3, 9 ,279 DATED August 5, 1975 |NVENTOR(S) Donald Irvin Hoke It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In column 23, lines 26-31, the portion of the formula reading N should read N lines 37-38, "with sodium" should read -which comprises.

Signed and Scaled this Attesl:

RUTH C. MASON C. IAISIIALLDANN A Nesting Uffifl" (ummissionu of Parents and Trldenllrks 

1. A COMPOUND OF THE FORMULA: WHEREIN R'' IS A HYDROCARBON RADICAL, EACH OF R2, R3, R4, AND R5 IS INDIVIDUALLY HYDROGEN OR A HYDROCARBON RADICAL, AND R6 IS HYDROGEN OR A LOWER ALKYL RADICAL.
 2. A compound according to claim 1 wherein R1, R4 and R5 are alkyl radicals; R2 is hydrogen or an alkyl radical; R3 is hydrogen and R6 is hydrogen or methyl.
 3. A compound according to claim 2 wherein R1, R4 and R5 are lower alkyl radicals; R2 and R3 are hydrogen; and R6 is hydrogen or methyl.
 4. N-(1,1-Dimethyl-3-hydroxybutyl)acrylamide, the compound of claim 1 wherein R1, R4 and R5 are methyl and R2, R3 and R6 are hydrogen.
 5. N-(1,1-Dimethyl-3-hydroxybutyl)methacrylamide, the compound of claim 1 wherein R1, R4, R5 and R6 are methyl and R2 and R3 are hydrogen.
 6. A method for the preparation of a compound according to claim 1 which comprises reducing the carbonyl group of an N-3-oxohydrocarbon-substituted acrylamide of the formula
 7. The method of claim 6 wherein the reducing agent is sodium borohydride or a lower aliphatic alcohol in the presence of a metal alkoxide.
 8. A method according to claim 7 for the preparation of N-(1,1-dimethyl-3-hydroxybutyl)acrylamide with sodium reducing N-(1,1-dimethyl-3-oxobutyl)acrylamide with sodium borohydride.
 9. A method according to claim 7 for the preparation of N-(1,1-dimethyl-3-hydroxybutyl)methacrylamide which comprises reducing N-(1,1-dimethyl-3-oxobutyl)methacrylamide with sodium borohydride.
 10. A method for the preparation of a compound according to claim 1 which comprises (1) reacting an alcohol of the formula ROH, wherein R is a lower alkyl radical, with an N-3-oxohydrocarbon-substituted acrylamide of the formula
 11. The method of claim 10 wherein step (2) is accomplished by hydrogenation.
 12. The method of claim 11 wherein the hydrogenation is effected in the presence of a Raney nickel catalyst.
 13. The method of claim 10 wherein step (3) is accomplished by pyrolyzing the 3-alkoxypropionamide in the presence of strong alkali.
 14. A method according to claim 10 for the preparation of N-(1, 1-dimethyl-3-hydroxybutyl)acrylamide which comprises (1) reacting N-(1,1-dimethyl-3-oxobutyl)acrylamide with methanol in the presence of a strongly alkaline catalyst to form N-(1,1-dimethyl-3-oxobutyl)-3-methoxypropionamide; (2) reacting said N-(1,1-dimethyl-3-oxobutyl)-3-methoxypropionamide with hydrogen in the presence of Raney nickel to form N-(1,1-dimethyl-3-hydroxybutyl)-3-methoxypropionamide; and (3) removing the methoxy group therefrom by pyrolysis at about 150*-200*C. in the presence of strong alkali. 